Transfer paper



inn

vided state.

I Patented July 21,1953

assignors to h m lI'Cash-Register Com- Dayton, Ohio, a corporation ofMaryland j No Drawing. Application'June 28, 1951',

. Serial No. 234,161

This invention relates to a manifold sheet, and more particularlypertains to one having a transfer coating that is hydrophobic and whichcontains a colorless recording oil which carries a colorlesscolor-reactant material. The oil is carried in a low polar wax binder.The sheet is for use on specially sensitized paper usedas an under sheetand the recording oil is transferred to the under sheet in printing-andwriting operations in a manner similar to the way in which'transfer ofcoloring material is made from a carbon transfer sheet, the only colorproducing material being the color reactant carried in the oil. Inmaking carbon transfer sheets which have'a wax coating containing acolored dye or pigment, oil is sometimes used with the wax to-plasticizeit so that it will transfer better, but the oil plays no part in causingthe colored mark, such being made by the colored Wax. The fact that thewax, oil, and

color-reactant carried by the oil, are all hydrol phobic, renders thetransfer sheet immune to the effects of humidity. The color reactantsare so chosen as to need no moisture for the creation of color on theunderlying sheet.

2 Claims. (o1.117 ss) sheet onto 'an'under sheet, except that in thesheet of this invention the wax is colorless and plays no part incausing a mark on the under .actant. ;the oil are aromatic double-bondorganic comment acts as an electron'acceptor with reference to the colorreactant material carried by the oil, and is an adsorbent with respectto such color re- 1 The color reactant materials carried by pounds,normally colorless, which upon adsorption on the pigment are convertedto a more highly polarized conjugated form, accompanied by theappearance of color. This color reaction phe- I ;nomenon is also fullyset forth in the patent to which reference has been made. Examples ofthe l organic color reactant will be given in the description to follow.'Several of the most. important features of the novel transfer sheet arethat itmay be handled Without discoloring the hands. It may be rubbedontoan unsensitized surface without leaving a mark. It is immune tohumidity and it has a clean colorless appearance which is strikinglydifferent from ordinary carbonmanifold transfer sheets heretofore known.The marks made on the sensitized under sheet requiring the presence,..

' in adsorption contact, of theacid-like pigment;

The sensitized under sheet with which the 7 novel manifold sheet isintended to be used is sensitized by particles of acid-like, inorganicma- 1 terial, also colorless or nearly so in the finely di- Typical ofsuch sensitizing pigments are ,attapulgite; sodium ,zeolitematerial;sodium zeolite material in which the natural sodium. exchange ions havebeen replaced by the ions of hydrogen, nickel, copper, iron, zinc, iner-V cury, barium, lead; cadmium, and potasfsiumf halloysitej and magnesiumtrisilicate'. These 7 pigments in finely divided form, either singly ormixed, may be applied to the paper in a suitable paper coating bindermaterial, such as paper coating starch, casein, or latex, the proportionof pigment to binder material being such that a large proportion of thesurface area-of the. pig; .ment particles'is exposed for contact byvthere cording oiltransferred thereto by the novel mania fold sheet. Thepigment materials mentioned are practically colorless and'give the sameeffect and adhere to the paper as does ordinary paper coating clay;Thesensitized receivingsheet is more fully described in United StatesPatent 2,548,364, which issuedf on the application of 7 Greenand'Sandberg. The color reactioninwhichthefoilecarried color-reactanttakes part is a socalled adsorption color: reactionin whichtheypigk forthe appearance of color, will not come off onto the. hands of a personwho makes contact with the colored marks, any oil thatis unused whenrubbed off from the under sheet being colorless, andany of the reactantcolor-reactant material which may be desorbed from the receiving sheetlosing its color and reverting to the original cola orlessstate. Itwillbe seen, therefore, that there are'uses for the novel manifold sheetin which these characteristics are of great value a's, for instance,inthe fieldof sales books, in which a duplicate copy of 'asales entry ismade on the underlying sheet by means of amanifold transfer coating. Themanifold sheet which constitutes the original entrywill have on its backthe transfer coating, but it is colorless, will not be rubbed off by wethands and may be safely placed with white merchandise without smudgingsuch, Moreover, the copy on which the, marks were made by the transfercoating may be safely placed with such white merchandise withoutdiscoloring it because, as has been said, the wax which may heaccidentally rubbed off is colorless, or nearly so, and contains nocolored material, all the color in the mark being in the color reactantwhich is absorbed and attache'dto the'pigment particles I which arefound upon the receiving sheet. Again,

inthisrespect, this manifold sheet differs from carbon paper in that themarks made by-carbon paper may rub off the receiving sheet with the wax,carrying with it the coloring material,

- mud in w at rem mes in .wni q e ewith...

hydrophyllic colloid film in which were dispersed discrete fluidinclusions of an oil which. contained either a coloring material in thecolored form or a color-reactant. of the useful color-reactantmaterials, the compound tetra-methyl-diaminodiphenyl-phthalide,

which is commonly known as malachite green lactone, having the molecularformula 3,3 bis (p-dimethylaminophenyl) phthalide. That com.- pound isalso useful in the transfer coating of this invention, but it is carriedin a Wax binder and not in the form of liquid droplets in a hydrophyllicbinder, the wax being hydrophobic. Neither should the transfer coatingor film. of this invention be confused with the transfer coating set outin United States Patents 2,550, l66 to 2,550,473 inclusive, whichdisclose a rupturable film containing droplets, the film being of ahydrophyllic nature. In the patents to which reference was made, andwhich disclose a transfer coating consisting of a rupturablehydropliyllic film containing droplets, the transfer coating was made bydeposition on paper of an emulsion having an external phase which isdryable to form the rupturable film and an oil internal phase, carryingthe color, which remains in the dry film as droplets. The external phaseis a solution of hydrophyllic colloid material in water and the coatingdries to a film by evaporation of the water. In the manifold sheet ofthis invention the transfer film is applied as a hot melt coating whichsolidifies by cooling, and the oil is not contained in droplets but iscombined with the wax as an intimate mixture of two hydrophobicmaterials.

The hydrophobic wax must be chosen so as not to have a tendency to coatover the active surfaces of the pigment particles, and the wax must holda high content of the recording oil. Moreover, the wax must be of lowpolarity so as not to interfere with the color reactant, and it must beresistant to smudging action when resting on an underlying receivingsheet under moderate pressure. It will be appreciated that in markingand printing operations, the pressure per unit area is many times thatwhich is obtained by mere stacking of the papers together. Anotherobstacle to be overcome is that the sensitizing materials on theunderlying sheets are selected because of their adsorbent nature andhence they tend to draw out the oil from the transfer film in contacttherewith and such film must be highly resistant to such adsorbenteffect.

Therefore, it is an object of this invention to provide a manifold sheethaving a transfer film including oil intimately mixed with a wax binder,said oil containing a colorless adsorbate colorreactant, for use onrecord material with a highly adsorbent" pigment which causes theab'sorbate to assume adistinctive color when in adsorption contacttherewith.

Another object of the invention is to provide such a manifold sheet'inwhich the film mate- That patent indicated as one:

rials, including the wax, oil and color-reactant, are all hydrophobicmaterials.

A still further object of the invention is to provide such a system inwhich, by the addition of inert particle material thereto, theresistance of the transfer film to smudging is increased.

With these and incidental objects in view, the invention includescertain novel features and combinations of ingredients, a preferred formor embodiment of which is hereinafter described in detail.

General description In the preferred embodiment of the invention,

about 55%, by weight, of colorless oil containing the hydrophobiccolor-reactant is mixed with 45%, by weight, of wax. The percentage ofoil with respect to the wax may vary from 25%, by weight, to by weight.The colorless oil with reactant is made up of 94%, by weight, ofpetroleum lubricating oil of a 200 seconds Saybolt viscosity, and 6%, byweight, of the color reactant which is made up of one-half crystalviolet lactone and. one-half benzoyl leuco methylene blue. The crystalviolet lactone is 3,3 bis (p-dimethylaminophenyl fi-dimethyl-aminophthalide, and

may be made by the method disclosed in United States Patent Re. 23,024,which issued on the application of Clyde S. Adams. tone has thefollowing structure:

N(CH3):

The benzoyl leuco methylene blue has the following structure:

cane wax, another 4/9 being fully refined parainn wax, and 1/9 beinglvlontan wax. The wax is heated until it is melted to a consistencywhere it can be readily stirred and the oil, with the color reactanttherein, is added and the mixture thoroughly stirred until theingredients are homogeneously integrated. This mixture, While still inthe melted condition, is applied as a coating on paper in the samemanner as wax-base carbon paper coatings are applied, and to acomparable Crystal Violet Lac- 36 x48" being sufficient; although'm'oreor'less" I may be applied, ;This;-coating ;is discernible on the paper,not b'y its color; but by the textureof the surface and its lightreflecting qualities.

In a second embodiment- 0f thein'vention "58%, by weight, ofthecolorless recording )il,-i's ;used

with 22%, by weight, of Ouricurywax'and20%1 'of fully refinedparaifihwax, and this is used in the same manner as the mixture of the preferredembodiment. I

In the third embodiment of the invention 55 by weight, of the colorlessrecording oil -ism'ixed with 45%, by weight, ofgCarnauba wax;

In a fourth embodiment of the invention. 60%, by weight, of thecolorless recording oil isused with25%, by weight, of Ouricury-wax and15.%', by Weight, of montan wax. 'In this embodiment, the colorless oilis 75%,"b3i'vi7e'ight, of thesiamje kind of petroleum lubricating oilmentioned in the preferred embodiment, and 25%, by weight,

I 6 I I and which turns from a normally colorless 'state': to dark blueon the sensitized record material.

"(0') "Malachite green lactone, which is 3,3 bis-(p-dimethylam'inophenyl) 'pnth'alide', having thestructure ofchlorinated diphenyl of a chlorine content of 65%. The color reactantsmaybe .used in the same amount as described for the preferredembodiment. The resinous character of the chlorinated diphenyl helpsprevent smudge. I

The wax may be modified by use of other resinous material thanchlorinated diphenyl to increase smudge resistance, coumarone indenebeing suitable.

In a fifth embodiment, 50%, by weight, of the colorless recording oil ofthe preferred embodiment is mixed with by weight of montan wax, and 25%,by weight, of fully refined parafiin wax.

In all of the above embodiments, inert fillers to the extent of 5% to15%, by weight, of the coating may be incorporated into the mixture todecrease the possibility of smudge when in stor agecontact with thesensitized paper with which it is to be used. Mineral fillers, such astitanium dioxide, calcium carbonate, and barium sulphate,

are satisfactory, but hydrophobic carbethoxylated starch derivativessuch as sold by the National Starch Company, under the'name of Dryfio,have been found to be of exceptional merit. I

Following are some hydrophobic color-reactants, among the manyavailable, which may be used alone or substituted for the crystal violetlactone with the benzoyl leuco methylene blue, which have beenpreviously specified: g (a) Xanthene-Qp-benzoic acid,3,6-bis-diethylamino 9 p-nitroanilino lactam, having the structure I f\ITTONO:

and which turns from a normallycolorless. state to red on the sensitizedrecord material.

(b) Michlers hydrol, which is, bis(p-dimethylaminophenyl) methanol,having the structure Fahrenheit, and fatty-acid amides.

I I having the structure I which 'chang'es from its normally colorlessstate to green-onsensitimd paper. p I

(103,3 bis(p diethylaminophenyl) phthalide;

(mnemmoire which changes from its normally colorless state to blue-greenon'sensitized paper.

(e) 3,3 bis(p-di-n propylaminophenyl) phthalide,v having the structurewhich changes from its normally colorless state to deep green onsensitized paper.

As substitutes for the petroleum oil mentioned are the'chlorinated oralkylated diphenyls havsistance required.

It will be evident from the foregoing that the novel manifold sheet maybe made from many substances, and that the invention does not residewith the particular oils, waxes, and color reactants used,except fortheir characteristics of miscibility, hydrophobic nature, lack of color,and consistency for' use as transfer materials useful in printing andWriting.

While the embodiments of the'invention herein described are admirablyadapted to fulfill the objects primarily stated, it is to be understoodthat it is not intended to confine the invention to the particularingredients or embodiments herein disclosed, for the invention issusceptible of embodiment in various other forms.

What is claimed is:

1. A manifold sheet for use in conjunction with a copy-receiving sheetsensitized on the copy-receiving surface thereof with particles ofinorganic clay-like material, said particles having acid-like adsorbentsurfaces, including a base web; and a film on said web of asubstantially colorless hydrophobic low polarity wax having mixedtherein a substantially colorless atmospherically stable hydrophobic oilcontaining a substantially colorless hydrophobic double bond aromaticatmospherically stable adsorbate compound, which organic compound isconverted to a more highly polar conjugated form accompanied by theappearance of a distinctive color therein when adsorbed on particles ofinorganic clay-like ma- 8 terial which acts as an electron acceptor withrespect to .said organic compound on adsorption contact therewith, andthe oil and adsorbate compound being to of the total weight of the film.

2. The sheet of claim 1 in which there is incorporated, with-the wax,oil and color reactant, a hydrophobic finely divided filler material.

CHESTER DAVIS.

NED A. THACKER.

References Cited in the file of this patent UNITED STATES PATENTS NumberName 0 Date 2,040,075 Brower May 12,1936 2,503,680 Newman Apr. 11, 19502,548,366 Green Apr. 10, 1951 2,554,909 Holik May 29, 1951

1. A MANIFOLD SHEET FOR USE IN CONJUNCTION WITH A COPY-RECEIVING SHEETSENSITIZED ON THE COPY-RECEIVING SURFACE THEREOF WITH PARTICLES OFINORGANIC CLAY-LIKE MATERIAL, SAID PARTICLES HAVING ACID-LIKE ADSORBENTSURFACES, INCLUDING A BASE WEB; AND A FILM ON SAID WEB OF ASUBSTANTIALLY COLORLESS HYDROPHOBIC LOW POLARITY WAX HAVING MIXEDTHEREIN A SUBSTANTIALLY COLORLESS ATMOSPHERICALLY STABLE HYDROPHOBIC OILCONTAINING SUBSTANTIALLY COLORLESS HYDROPHOBIC DOUBLE BOND AROMATICAT-LY MOSPHERICALLY STABLE ADSORBATE COMPOUND, WHICH ORGANIC COMPOUND ISCONVERTED TO A MORE HIGHLY POLAR CONJUGATED FORM ACCOMPANIED BY THEAPPEARANCE OF A DISTINCTIVE COLOR THEREIN WHEN ADSORBED ON PARTICLES OFINORGANIC CLAY-LIKE MATERIAL WHICH ACTS AS AN ELECTRON ACCEPTOR WITHRESPECT TO SAID ORGANIC COMPOUND ON ADSORPTION CONTACT THEREWITH, ANDTHE OIL AND ADSORBATE COMPOUND BEING 25% TO 75% OF THE TOTAL WEIGHT OFTHE FILM.